The Italian full-back becomes Reds boss Rafa Benitez's second signing of the summer following the arrival of Swiss international Philipp Degen on Thursday.
The left-back will compete with Fabio Aurelio for a place in Liverpool's first XI and is viewed as a replacement for John Arne Riise, who recently moved to Roma.
Reports suggest that the 26-year-old has cost Liverpool a fee in the region of £7million.